Color photography



Patented Jan. 9, 1940", I

UNITED STATES,

@1108 PHOTOGRAPHY Wilhelm Schneider and Alfred Walnut:

Germany, salmon, by memo assignments, 5 Me Anaco Corporation,Binghamton. N. 1., a

corporation of Delaware o Drawing. Application September 18, 1987.sa-hi9 No. 184,409.11: Germany October I,

is calm. (01. 05-0) Our present invention relates to color photographyand more particularly to improved color components for the process ofcolor development.

It has for an object to provide color components which are soluble inwater and which are fast to diffusion with respect to the silver halideemulsion.

A further object of the invention is to provide a new and improvedprocess for preparing color formers having these properties.

A further object is to provide silver halide emulsions containing thecolor components fast to diffusion.

A further object is to provide an improved film for color photographyhaving superposed silver halide emulsion layers, each layer containing acolor component fast to diflusion.

A known process for producing color photographic and cinematographicpictures uses silver halide emulsion layers which contain color formers.The production of the picture varies with the kind of color former used.As described in U. 8. Patents 1,102,028 and 1,055,155 there may be usedcolor formers which yield color pictures during the development withcertain developing substances. For producing multi-color pictures it hasbeen proposed to superimpose lightsensitive. layers containing variouscoupling bodies, the layers being separated from each other: byintermediate layers so that difiusion oi the coupling bodies from thelight-sensitive layers may be prevented. It hasbeen found,however, thatthis expedient for preventing difiusion is not sufliciently successfulin practice. In U. S. Patents 2,179,228, 2,178,612, and 2,179,244 and U.S. patent applications Ser. No. 94,340 filed August 5, 1936, and Ser.No. 159,518, filed August 17, 1937, there are described dyestuil'components which are fast to diffusion. I

The present invention is based on the observation that, color formers ofgood fastness to diffusion are obtainable by the introduction into themolecule of the dyestufi component as a substituent, a constituent or aconversion product of a natural resin. The conversion products, however,are limited to those in which the' general structure of the naturalresin is substantially retained. The constituent or conversion productof the natural resin must contain a reactive group, for instance acarboxyl group or a hydroxyl group, with the aid of which the colorformer can be caused to enter into chemical combination. Suitableresinous products are, for example, a-pimarabietic acid, fl-pimarabieticacid, pinabietic acid, abietic acid, dihydropinabietic acid,siaresinolic acid, sumaresinolic acid, a-amyrin and various resinolesand bitter substances, for example the humulone of hops.

The compounds of the resinous product with the dyestuil former may bemade in known manner, either by producing an ester-like or acidamide-like union between the hydroxyor the amino-group of the dyestuifformer and the acid 5 group of the resin acid or by producing anetherlike union, for instance between the hydroxygroup of the resinoleand the 'hydroxy-group oi the dyestufl former. For further guidance tothose skilled in the art reference is here made to the examples, whichdisclose in detail the actual process to be followed. They do not,however, limit the invention to the specific data disclosed there, butall such equivalent processes are within the ambit of the invention asfall within the scope of the annexed claims.

-As dyestuil components into which the residue of the resin product isto be introduced there may be named, for example, aminonaphthols,

When the dyestufi component of this kind, that is to say containing aresin constitution, is added to a photographic silver halide emulsionthe 001- or picture may be produced, according to the nature of thedyestufi' component, by color development or through the intermediary ofdiazo-compounds or by the silver bleaching-out process. The proceduremay be that described in any of the following: U. S. Patent 2,179,228and U. S. patent application Ser. No. 141,093, filed May 6, 1937, and inany of the U. S. patents or U. S. patent applications enumerated on page1, column 1, lines 35 to 38. Or the components located in multi-layerfilm may be converted into azo-dyes following development and fixing bytreatment with a diazo compound such as a carbonic acid solution oftetrazotized benzidine disulfonic acid.

' to oduce the dye image.

The dyestuff formers used in the foregoing process are, in consequenceof the groups in the dyestufi molecules which lend solubility in water,

of themselves or in the form of their salts soluble in water and maytherefore be incorporated without difliculty in the photographic silverhalide emulsion at any point in the process of the production. Theresinous substituent makes the dyestufl component fast to diffusion. Itmust be observed, however, that the chlorides of the resin acids must beused as homogeneous compounds.

The silver halide emulsions made in accordance process, for example bymordant dyeing or toning.

The emulsions may be prepared in any other manner, for exampledifferently sensitized emulsions having diflerent dyestufl formers maybe brought in the term 01 small particles on the surface 01' thecarrier.'

The iollowing examples illustrate the invention:

(1) 30 grams or the purest colophony are converted in known manner intoabietic acid chloride and the benzene solution of this is added in dropsto a solution of 18 grams or ,1-amino-5- naphthol in 100 cc. 0! pyridineso that by application of external heat the benzene dropped in iscontinuously distilled off. when all the aminonaphthol has entered intoreaction with the abietic chloride the product is precipitated by meansof ice anda'iter the mass has been rendered acid to Congo byhydrochloric acid it is filtered and the solid matter washed. 1 Thelatter is the dyestufi component which is to be added to the silverhalide emulsion.

(2) grams of 3f-amino-5'-sulio- -phenyl- 3-methyl-5-pyrazolone aredissolved in 100 cc. of pyridine. Into the solution there is dropped asolution of grams 0! abietic acid chloride in benzene, the additionbeing so made that the benzene is continuously distilled oil. When allthe aminosuliophenylpyrazolone has entered into reaction the whole isprecipitated by means of ice, then made acid to Congo by means ofhydrochloric acid and filtered, the solid matter being washed neutralwith water.

20 grams of the dyestuif component thus obtained are added to 1 kilo oiemulsion and the latter is then poured to form a layer. After exposurethe layer is developed with a solution alkaline with sodium carbonate ofaminodimethylaniline, whereby there is obtained a red color image inaddition to the silver image. The latter is removed in known manner,whereby the red color image remains.

If the exposed silver halide emulsion layer is developed not withaminodimethylanillne but with an ordinary black-and-white developer andthe silver image is converted into a silver antidiazotate ofs-naphthyl-amine, for example as described in U. S. patent applicationSer. No. 10,704, filed March 12, 1935, and finally this antidiazotatesilver image is treated with a weak acid solution, a yellow picture isobtained.

Instead of converting the silver image into the diazo-image there may beproduced throughout the whole layer a uniform red dyestui! by treatingthe layer with a solution of tetrazotized benzidine disulfonic acid anddestroying the red dyestuff at the places of the silver image by thesilver bleaching out process with use oi! known agents.

(3) A three-layer film for three-color photography is made in thefollowing manner.

1 kilo of silver bromide emulsion is mixed with 15 grams ofpara-abietylaminobenzoylacetic acid anilide-para-carboxylic acid. In thelayer 01 this emulsion there may be produced by means or colordevelopment a yellow dyestufl image.

Also dyestufl images which may be produced with aid 01 diam-compoundsare yellow.

. thereto by For making the second-emulsion layer 1 kilo or silverbromide emulsion is mixed with a sensitizer for green and then with'liigrams of a solution 01 3-abietylamino-fi-sulio-l-phenyl-S-methyl-fi-pyrazolone. In this layer there is produced by colordevelopment a purple dyestui! image.

For making the third emulsion layer 1 rub of silver bromide emulsion ismixed with a sensitizer for red and with a solution of 15 grams of labietylamino 5 hydroxynaphthalene-B-carboxylic acid. In this layerchromogenic development produces a blue-green dyestufl image.

I! desired the several layers oi. emulsion may be alternated with filterlayers.

What we claim is:

1. A photographic silver color photography comprising naphthol.

2. A photographic silver halide emulsion for color photographycomprising 3-abietyl-amino- 5-sulio-1-phenyl-3-methyl-fi-pyrazolene.

3. A silver halide emulsion for color photography containing a colorformer having a natural resin linked thereto by a homopolar linkage.

4- A silver halide emulsion tor color photography containing a colorformer having .a natural resin linked thereto by a homopolar linkage,said natural resin being a member oi! the group consisting ofpimarabietic acid, pinabietic abietic acid, slaresinolicandsumareslnolic acids, amyrins, resinoles and humulones.

5. A silver halide emulsion for color photography containing a naturalresin-acid-amide 0! a color former.

6. A process which comprises developing with an aromatic amino developera silver halide emulsion for color photography containing a color formerhaving a natural resin linked thereto by homopolar linkages.

7. A process which comprises developing with an aromatic aminodeveloper, a. silver halide emulsion for color photography containing acolor former having a natural resin linked therehalide emulsion torabietyl-aminoto by homopolar linkage, said natural resin being acid,. 30

a member of the group consisting of pimarabietic" acid, pinabietic acid,and sumaresinolic acids, amyrins, humulones.

8. A process which comprises developing with an aromatic aminodeveloper, a silver halide emulsion for color photography containing anatural resin-acid amide of a color former.

9. The silver halide emulsion defined in claim 3 wherein the homopolarlinkage is selected from the class consisting of an ether-, an ester-,and an acid amide linkage. I

10. The silver halide emulsion defined in claim abietic acid,siaresinolicresinoles and 5 wherein the resin acid is abietic acid.

11. The silver halide emulsion defined in claim- 5 wherein the colorformer is a pyrazolone and the resin acid is'abietic acid.

12. A photographic silver halide gelatine emulsion Iorcolor photographycomprising abietylaminosuliophenylpyrazolone. 1

13. A silver halide emulsion for color photography containing a colorformer having linked a homopolar linkage a resinous substance selected'from stantially retained. I

the class consisting of a 7. natural resin and its derivatives in whichthe molecular structure of said natural resin is sub-

